Polyether polyol composition and use thereof

ABSTRACT

A polyether polyol composition comprising: a polyether polyol, a phosphoric acid compound selected from the group consisting of at least one of orthophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and partial esters thereof in an amount raning from 0.5 to 100 ppm based on the polyether polyol metals derived from a composite metal cyanide complex catalyst in an amount ranging from 1 to 30 ppm based on the polyether polyol; a method for producing this polyether polyol composition; and methods of making polyurethane or isocyanate group-terminated prepolymers.

TECHNICAL FIELD

The present invention relates to a polyether polyol produced by acomposite metal cyanide complex catalyst and use thereof.

BACKGROUND ART

Heretofore, a polyether polyol as a material for polyurethaneelastomers, adhesives, sealants, etc., has been produced by polymerizingan alkylene oxide such as ethylene oxide or propylene oxide by means ofan initiator having active hydrogen atoms. As a typical polymerizationcatalyst for an alkylene oxide, a composite metal cyanide complex(hereinafter referred to also as a DMC catalyst) is known. The DMCcatalyst is a catalyst comprising an organic ligand and a metal salt andis represented by a compound having an organic ligand, water and ZnCl₂coordinated on zinc hexacyano cobaltate (Zn₃[Co(CN)₆]₂).

In recent years, it has been reported that the catalytic life of a DMCcatalyst is remarkably prolonged by the use of tert-butyl alcohol as anorganic ligand (JP-A-4-145143). Further, JP-A-2000-513389 discloses thatby employing a highly active DMC catalyst using an organic ligand suchas tert-butyl alcohol, it is possible to reduce the amount of thecatalyst to be used, and it is possible to eliminate a step for removalof the DMC catalyst after the production of a polyether polyol.

And, JP-A-9-132630 discloses that it has been found that a polyetherpolyol having from 10 to 1,000 ppm of a residue of a DMC catalyst, or acomposition comprising such a polyether polyol and an antioxidant, has astorage stability, and with an isocyanate group-terminated prepolymerprepared by using such a polyether polyol or composition, the storagestability is not poor. Further, in JP-A-9-132630, a triester ofphosphorous acid is exemplified as an antioxidant. However, in order toobtain a sufficient storage stability, it is required to use theantioxidant in a large amount as much as at least 500 ppm.

On the other hand, it is known, for example, by JP-A-6-502674 (U.S. Pat.No. 3,391,101) that a phosphorus compound is used in a purification stepafter preparing a polyether polyol by means of a DMC catalyst having arelatively low activity, using glyme or the like as an organic ligand.JP-A-6-502674 discloses a process wherein a polyether polyol is producedusing about 500 ppm, based on the finally formed polyether polyol, of aDMC catalyst, and then the DMC catalyst is decomposed by an alkalicatalyst such as an alkali metal hydroxide, followed by neutralizationtreatment by means of a phosphoric acid compound, whereupon theneutralized salt is removed. Thus, it has already been known to use aphosphoric acid compound to neutralize an alkali used to deactivate theDMC catalyst in the process for removing the DMC catalyst.

Further, JP-A-5-170857 proposes that a thermally stable prepolymer canbe produced in the presence of from 100 ppm to 10% of an ester ofphosphorus acid during the preparation of the prepolymer by using theobtained polyether polyol.

DISCLOSURE OF THE INVENTION

The present invention is to solve the above-described problems and toprovide a polyether polyol which is a polyether polyol capable ofeliminating a step of removing the DMC catalyst and whereby, when formedinto an isocyanate group-terminated prepolymer, the storage stabilitywill not be deteriorated.

The present invention is the following invention which will solve theabove-mentioned problems.

A polyether polyol composition comprising a polyether polyol obtained byring-opening polymerization of an alkylene oxide in the presence of acomposite metal cyanide complex catalyst, and a phosphoric acid compoundcomprising a phosphoric acid selected from orthophosphoric acid,polyphosphoric acid and polymetaphosphoric acid, and/or a partial esterof such a phosphoric acid, characterized in that the polyether polyolcomposition contains metals derived from the composite metal cyanidecomplex catalyst in an amount of from 1 to 30 ppm based on the polyetherpolyol, and the above phosphoric acid compound in an amount of from 0.5to 100 ppm based on the polyether polyol.

A polyurethane resin obtained by reacting the above polyether polyolcomposition with a polyisocyanate.

An isocyanate group-terminated prepolymer obtained by reacting the abovepolyether polyol composition with a polyisocyanate.

A method for producing a polyether polyol composition, which comprisesproducing a polyether polyol by ring-opening polymerization of analkylene oxide in the presence of a composite metal cyanide complexcatalyst in such an amount that the metals derived from the compositemetal cyanide complex catalyst would be from 1 to 30 ppm based on thefinally formed polyether polyol, and then adding a phosphoric acidcompound comprising a phosphoric acid selected from orthophosphoricacid, polyphosphoric acid and polymetaphosphoric acid, and/or a partialester of such a phosphoric acid, in an amount of from 0.5 to 100 ppmbased on the polyether polyol, without via a step of removing thecomposite metal cyanide complex catalyst.

A method for producing a polyurethane, characterized by producing apolyether polyol by ring-opening polymerization of an alkylene oxide inthe presence of a composite metal cyanide complex catalyst in such anamount that the metals derived from the composite metal cyanide complexcatalyst would be from 1 to 30 ppm based on the finally formed polyetherpolyol, then adding a phosphoric acid compound comprising a phosphoricacid selected from orthophosphoric acid, polyphosphoric acid andpolymetaphosphoric acid, and/or a partial ester of such phosphoric acid,in an amount of from 0.5 to 100 ppm based on the polyether polyol,without via a step of removing the composite metal cyanide complexcatalyst, to obtain a polyether polyol composition, and further reactingthe polyether polyol composition with a polyisocyanate.

A method for producing an isocyanate group-terminated prepolymer,characterized by producing a polyether polyol by ring-openingpolymerization of an alkylene oxide in the presence of a composite metalcyanide complex catalyst in such an amount that the metals derived fromthe composite metal cyanide complex catalyst would be from 1 to 30 ppmbased on the finally formed polyether polyol, then adding a phosphoricacid compound comprising a phosphoric acid selected from orthophosphoricacid, polyphosphoric acid and polymetaphosphoric acid, and/or a partialester of such phosphoric acid, in an amount of from 0.5 to 100 ppm basedon the polyether polyol, without via a step of removing the compositemetal cyanide complex catalyst, to obtain a polyether polyolcomposition, and further reacting the polyether polyol composition witha polyisocyanate.

EFFECTS OF THE INVENTION

By using the polyether polyol produced by the composite metal cyanidecomplex catalyst of the present invention, the reaction rate with apolyisocyanate can be controlled, and it is possible to produce aprepolymer or a polyurethane having a high storage stability.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows the relation between the reaction time (hr) and theisocyanate reaction rate z (%).

BEST MODE FOR CARRYING OUT THE INVENTION

Composite Metal Cyanide Complex Catalyst

In the present invention, a polyether polyol composition contains metalsderived from a composite metal cyanide complex catalyst in an amount offrom 1 to 30 ppm, preferably from 2 to 20 ppm, particularly preferablyfrom 3 to 15 ppm, based on the polyether polyol. If the metals derivedfrom the composite metal cyanide complex catalyst are in an amountexceeding 30 ppm, control of the reaction at the time of producing apolyurethane from a polyether polyol, tends to be difficult. Further,the stability of a prepolymer obtained from such a polyether polyoltends to be poor, and the mechanical properties of a polyurethane tendto be adversely affected. On the other hand, if their amount is lessthan 1 ppm, the viscosity of the polyol tends to be remarkably high,whereby the handling tends to be difficult.

Composite Metal Cyanide Complex Catalyst

A composite metal cyanide complex catalyst is typically represented bythe following formula (1).M¹ _(a)[M² _(b)(CN)_(c)]_(d)e(M¹ _(f)X_(g))h(H₂O)i(R)  (1)(wherein each of M¹ and M² is a metal, X is a halogen atom, R is anorganic ligand, and each of a, b, c, d, e, f, g, h and i, is a numberwhich is variable depending upon the atomic balances of metals, thenumber of organic ligands to be coordinated, etc.)

In the above formula (1), M¹ is preferably a metal selected from Zn(II),Fe(II), Fe(III), Co(II), Ni(II), Mo(IV), Mo(VI), Al(III), V(V), Sr(II),W(IV), W(VI), Mn(II), Cr(III), Cu(II), Sn(II) and Pb(II), particularlypreferably Zn(II) or Fe(II). In the above formula, M² is preferably ametal selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III),Mn(II), Mn(III), Ni(II), V(IV) and V(V), particularly preferably Co(III)or Fe(III). II, III, IV and V in the above brackets represent the atomicvalences.

In the above formula (1), R is an organic ligand and is preferably atleast one compound selected from the group consisting of an alcohol, anether, a ketone, an ester, an amine and an amide. As such an organicligand, a water-soluble one is preferred. Specifically, one or morecompounds selected from tert-butyl alcohol, n-butyl alcohol, iso-butylalcohol, tert-pentyl alcohol, iso-pentyl alcohol, N,N-dimethylacetamide, glyme (ethylene glycol dimethyl ether), diglyme (diethyleneglycol dimethyl ether), triglyme (triethylene glycol dimethyl ether),ethylene glycol mono-tert-butyl ether, iso-propyl alcohol and dioxane,may be mentioned. The dioxane may be 1,4-dioxane or 1,3-dioxane and ispreferably 1,4-dioxane.

A particularly preferred organic ligand is one or more compoundsselected from tert-butyl alcohol, tert-pentyl alcohol and ethyleneglycol mono-tert-butyl ether, and tert-butyl alcohol or a mixture oftert-butyl alcohol with ethylene glycol mono-tert-butyl ether, is mostpreferred.

The composite metal cyanide complex catalyst can be produced by a knownproduction method. For example, it can be produced by a method whereinan organic ligand is coordinated to a reaction product obtained byreacting a metal halide with an alkali metal cyano metalate in anaqueous solution, then the solid component is separated, and theseparated solid component is washed with an organic ligand aqueoussolution, or a method wherein a metal halide is reacted with an alkalimetal cyano metalate in an organic ligand aqueous solution, and theobtained reaction product (solid component) is separated, and theseparated solid component is washed with an organic ligand aqueoussolution.

As the metal for the metal halide, one exemplified above as M¹ may bementioned, and Zn(II) or Fe(II) is particularly preferred. The mostpreferred as the metal halide is ZnCl₂. As the metal constituting thecyano metalate or the alkali metal cyano metalate, one exemplified aboveas M² may be mentioned, and Co(III) or Fe(III) is particularlypreferred. A preferred specific example of the alkali metal cyanometalate is Na₃[Co(CN)]₆ or K₃[Co(CN)]₆. Further, instead of the alkalimetal cyano metalate, H₃[Co(CN)₆] may also be used.

Further, the reaction product obtained by the above method may be washedand then subjected to filtration, and the cake (solid component) therebyobtained may be dried to prepare a composite metal cyanide complexcatalyst. Otherwise, the organic ligand aqueous solution containing thecomposite metal cyanide complex catalyst after washing the reactionproduct, may be dispersed in a polyol, and then, an excess amount ofwater and the organic ligand may be distilled off to prepare a compositemetal cyanide complex catalyst in a slurry form.

As the polyol to be used here, a polyether polyol may be mentioned. Thepolyether polyol is preferably a polyether polyol having from 2 to 12hydroxyl groups and a molecular weight of from 300 to 5,000 which isobtainable by ring-opening polymerization of an alkylene oxide with apolyhydric alcohol such as ethylene glycol, propylene glycol, diethyleneglycol, dipropylene glycol, trimethylol propane or glycerol in thepresence of an alkali catalyst or a cationic catalyst. Such a polyetherpolyol may be used also as an initiator at the time of subsequentlyproducing a polyether polyol.

The number of hydroxyl groups is preferably from 2 to 8, particularlypreferably from 2 to 3. The alkylene oxide is preferably an alkyleneoxide having at least 2 carbon atoms, and propylene oxide, 1,2-butyleneoxide, 2,3-butylene oxide, epichlorohydrin, oxetane or tetrahydrofuranmay, for example, be mentioned. They may be used in combination as amixture of two or more of them. Propylene oxide is preferred.

Polyether Polyol

In the present invention, the polyether polyol is produced byring-opening polymerization of an alkylene oxide in the presence of theabove composite metal cyanide complex catalyst. In such a ring-openingpolymerization reaction, an initiator is usually used.

As the initiator, a polyhydric alcohol such as ethylene glycol,propylene glycol, diethylene glycol, dipropylene glycol, trimethylolpropane or glycerol, or a polyether monool or polyether polyol havingfrom 2 to 12 hydroxyl groups and a molecular weight of from 300 to5,000, which is obtainable by ring-opening polymerization of an alkyleneoxide with such a polyhydric alcohol in the presence of an alkalicatalyst or a cationic catalyst, may be mentioned. The number ofhydroxyl groups is preferably from 2 to 8, particularly preferably from2 to 3. The hydroxyl value of the initiator is at least twice,preferably at least three times the hydroxyl value of the polyetherpolyol as the final product. Further, as the initiator, a polyesterpolyol or a polycarbonate polyol may also be used.

The initiator may be introduced continuously to the reactor togetherwith an alkylene oxide and/or the catalyst, to carry out thepolymerization of the alkylene oxide. As the initiator which may be usedin such a case, a polyhydric alcohol having a low molecular weight maybe used. As such a polyhydric alcohol having a low molecular weight, apolyhydric alcohol having a molecular weight of at most 400, such asethylene glycol, propylene glycol, diethylene glycol, dipropyleneglycol, trimethylol propane or glycerol, may be mentioned.

With respect to the alkylene oxide to be added to the initiator, thealkylene oxide is preferably an alkylene oxide having at least 3 carbonatoms, and propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,epichlorohydrin, oxetane, or tetrahydrofuran may, for example, bementioned. They may be used in combination as a mixture of two or moreof them. Propylene oxide is preferred. Further, it is difficult to letethylene oxide react by itself, but it may be polymerized by adding itto the reaction system as mixed with an alkylene oxide having at least 3carbon atoms. A particularly preferred alkylene oxide is propylene oxideor a combination of propylene oxide and ethylene oxide. Further, acyclic ester such as lactone may be used in combination with thealkylene oxide.

The polyether polyol in the present invention is preferably a polyetherpolyol which is not subjected to a step of removing the catalyst afterring-opening polymerization of the alkylene oxide.

Accordingly, it is preferred to use the composite metal cyanide complexcatalyst in an amount such that the metals derived from the compositemetal cyanide complex catalyst would be from 1 to 30 ppm based on thefinally formed polyether polyol. The amount is preferably from 2 to 20ppm, particularly preferably from 3 to 15 ppm.

If the metals derived from the composite metal cyanide complex catalystare in an amount exceeding 30 ppm, the cost for the catalyst increases.Further, it tends to be difficult to control the reaction at the time ofproducing a polyurethane from the polyether polyol. Further, thestability of the prepolymer obtained from the polyether polyol tends tobe poor, which adversely affects the mechanical properties of thepolyurethane. Further, if their amount is less than 1 ppm, the viscosityof the polyol tends to remarkably increase, whereby the handling tendsto be difficult.

Further, the catalyst may be introduced into the reaction system all atonce at the beginning or may be introduced sequentially in a dividedfashion.

The average number of functional groups in the polyether polyol of thepresent invention is preferably from 2 to 12, more preferably form 2 to8, further preferably from 2 to 4. Further, the hydroxyl value ispreferably from 5 to 100, more preferably from 5 to 70, particularlypreferably from 5 to 35. Further, the total unsaturated degree ispreferably at most 0.07 meq/g, particularly preferably at most 0.03meq/g. There is no particular lower limit, but the lower limit ispreferably 0.003 meq/g.

Phosphoric Acid Compound

The polyether polyol composition in the present invention contains aphosphoric acid compound comprising a phosphoric acid selected fromorthophosphoric acid, polyphosphoric acid and polymetaphosphoric acid,and/or a partial ester of such a phosphoric acid, in an amount of from0.5 to 100 ppm based on the polyether polyol.

If the content of the phosphoric acid compound exceeds 100 ppm, it tendsto be difficult to control the reaction of the polyol with apolyisocyanate. Further, also in a case where it is less than 0.5 ppm,it tends to be difficult to control the reaction of the polyol with apolyisocyanate. The content of the phosphoric acid compound ispreferably at least 1 ppm. Further, it is preferably at most 50 ppm,particularly preferably at most 30 ppm.

Orthophosphoric acid (H₃PO₄) is a compound represented by [O═P(OH)₃].

Further, polyphosphoric acid is represented by the following formula(2):

(In the formula (2), n is an integer.)

As n, from 0 to 10 is preferred, and n is particularly preferably from 0to 5. Most preferred is pyrophosphoric acid (H₄P₂O₇) wherein n is 0,triphosphoric acid (H₅P₃O₁₀) wherein n is 1, or tetraphosphoric acid(H₆P₄O₁₃) wherein n is 2.

Further, polymetaphosphoric acid is represented by the formula (3):

(In the formula (3), m is an integer.)

As m, from 1 to 10 is preferred, and m is particularly preferably from 1to 5. Most preferred is trimetaphosphoric acid (H₃P₃O₉) wherein m is 1,or tetrametaphosphoric acid (H₄P₄O₁₂) wherein m is 4.

Each phosphoric acid selected from orthophosphoric acid, polyphosphoricacid and polymetaphosphoric acid is a polybasic acid wherein the numberof OH groups bonded to phosphorus atoms is at least 3, particularlypreferably a polybasic acid wherein the number of OH groups bonded tophosphorus atoms is from 3 to 6.

Further, in the present invention, a partial ester of such a phosphoricacid may also be used. The partial ester of a phosphoric acid means onewherein not all OH groups in the phosphoric acid are esterfied, and someOH groups remain. Namely, for example, a partial ester oforthophosphoric acid means a monoester of orthophosphoric acid or adiester of orthophosphoric acid.

The ester is preferably an ester having a C₁₋₁₈ hydrocarbon group, morepreferably one having a C₁₋₁₈ alkyl group, a C₁₋₁₈ cycloalkyl group or aC₁₋₁₈ aryl group.

The above alkyl group may, for example, be a methyl group, an ethylgroup, a propyl group, a butyl group, a hexyl group, an octyl group, a2-ethylhexyl group, a decyl group, a dodecyl group or a stearyl group.Further, it may be an alkyl group having an aromatic group as asubstituent, such as a benzyl group. The above aryl group is preferablya C₁₋₁₀ aryl group, and a phenyl group may be mentioned. Further, it maybe a group having an alkyl group as a substituent, such as a toluoylgroup or a xylyl group. The above cycloalkyl group may, for example, bea cyclopentyl group or a cyclohexyl group.

In a method for producing a prepolymer by reacting a polyether polyolwith a polyisocyanate, if a residue of a composite metal cyanide complexcatalyst remains in the polyether polyol, control of the reaction isconsidered to be difficult, as the metal component derived from such aresidue of the composite metal cyanide complex catalyst works as acatalyst for the urethane-forming reaction of the polyisocyanate withthe polyether polyol. In the present invention, the phosphoric acidcompound to be used is characterized in that it is a pentavalentphosphorus compound and it has OH groups, whereby it is considered thatby the oxidation reaction thereof, the remaining composite metal cyanidecomplex catalyst is deactivated.

Further, the effects of the present invention cannot be obtained with aphosphorus compound such as phosphorous acid or a phosphite. This isbelieved attributable to the fact that a phosphorus compound such asphosphorous acid or a phosphite has a strong reducing property, wherebydeactivation of the DMC catalyst tends to be difficult.

Further, even with a pentavalent phosphorus compound, if it is aphosphorus compound having no OH group, such as a triester oforthophosphoric acid, the effects of the present invention cannot beobtained. Thus, it is considered that such a phosphorus compound has noacidic proton and is not accordingly effective for deactivation of theDMC catalyst by oxidation.

In the present invention, the phosphoric acid compound and/or a partialester thereof is particularly preferably at least one member selectedfrom orthophosphoric acid, a monoalkyl ester of orthophosphoric acid anda dialkyl ester of orthophosphoric acid.

In the present invention, it is preferred that after the ring-openingpolymerization of an alkylene oxide in the presence of the compositemetal cyanide complex catalyst, the above phosphoric acid compound isadded without via a step of removing the catalyst.

The phosphoric acid compound may be added as it is or as diluted withwater or another solvent, and it is particularly preferred to add it inthe form of an aqueous solution. In a case where water or anothersolvent is used, such water or a solvent is preferably removed from thepolyol by drying under reduced pressure.

Uses

The polyether polyol composition of the present invention has an effectsuch that the reactivity with an isocyanate can easily be controlled. Apolyether polyol containing a metal component derived from a DMCcatalyst even in a very small amount, has had a problem that thereactivity with an isocyanate tends to be high, and the reaction ratecan hardly be controlled. However, according to the present invention,such a problem can be solved. Especially when it is reacted with apolyisocyanate compound to obtain an isocyanate group-terminatedprepolymer, such an isocyanate group-terminated prepolymer tends to behardly gelled thereby to provide an effect such that the isocyanategroup-terminated prepolymer is excellent in the storage stability. Thepresent invention provides an isocyanate group-terminated prepolymerobtained by reacting the above polyether polyol composition with apolyisocyanate.

The polyisocyanate which may be used, may, for example, be an aromaticpolyisocyanate such as tolylene diisocyanate, diphenylmethanediisocyanate or polymethylene polyphenyl isocyanate, an aliphaticpolyisocyanate such as hexamethylene diisocyanate, xylylenediisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate ortetramethylxylylene diisocyanate, an alicyclic polyisocyanate such asisophorone diisocyanate, or a modified product thereof.

The modified product may, for example, be a prepolymer modified productwhich is a reaction product of a low molecular weight diol with a lowmolecular weight triol, a buret product which is a reaction product withwater, or a trimer having an isocyanurate skeleton.

The isocyanate group-terminated prepolymer can be produced by reacting astoichiometrically excess amount of a polyisocyanate to the polyetherpolyol composition. It can be produced by thermally reacting thepolyoxyalkylene polyol composition with the polyisocyanate at atemperature of from 60 to 100° C. for from 1 to 30 hours in a drynitrogen stream in the presence or absence of a solvent and optionallyin the presence of a urethane-forming catalyst. The urethane-formingcatalyst is preferably an organometallic compound of e.g. tin, lead ortitanium. Particularly preferred is an organic tin compound, such asdibutyltin dilaurate, dibutyltin dioctoate or stannous octoate.

The isocyanate group-terminated prepolymer of the present invention canbe used for known uses. It can be used for a humidity curablecomposition which will be cured by a reaction with moisture in air, atwo-part curable composition to be reacted with a curing agent such as apolyamine, a polyether polyol or a low molecular weight polyol, acasting polyurethane elastomer, or other applications.

The present invention also provides a polyurethane resin obtained byreacting the above polyether polyol composition with a polyisocyanate.Such a polyurethane resin can be produced by a known method, and acuring agent such as a polyamine or a low molecular polyol, or the abovementioned urethane-forming catalyst may optionally be used.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples and Comparative Examples. However, it should beunderstood that the present invention is by no means restricted by suchExamples. Here, polyol X is a polyol having a hydroxyl value of 74.8,obtained by addition-polymerizing propylene oxide (hereinafter PO) todipropylene glycol by means of a KOH catalyst, followed by purificationby a known method.

Production of Composite Metal Cyanide Complex Catalyst

Reference Example 1

An aqueous solution comprising 10.2 g of zinc chloride and 10 g ofwater, was put into a 500 mL flask. An aqueous solution comprising 4.2 gof potassium hexacyano cobaltate (K₃CO(CN)₆) and 75 g of water, wasdropwise added to the aqueous zinc chloride solution in the above flaskover a period of 30 minutes with stirring at a rate of 300 rpm (numberof rotations/min). During this period, the mixed solution in the flaskwas maintained to be 40° C. After completion of the dropwise addition ofthe aqueous potassium hexacyano cobaltate solution, the mixture in theflask was further stirred for 30 minutes, whereupon a mixture comprising40 g of ethylene glycol mono-tert-butyl ether (hereinafter referred tosimply as EGMTBE), 40 g of tert-butyl alcohol (hereinafter referred tosimply as TBA), 80 g of water and 0.6 g of polyol X, was added, followedby stirring at 40° C. for 30 minutes and further at 60° C. for 60minutes. The obtained mixture was subjected to filtration under pressure(0.25 MPa) by means of a circular filter plate having a diameter of 125mm and a filter paper for fine particles (No. 5C, manufactured byADVANTEC) to separate a solid (a cake) containing the composite metalcyanide complex.

Then, the obtained cake containing the composite metal cyanide complexwas transferred to a flask, and a mixture comprising 18 g of EGMTBE, 18g of TBA and 84 g of water, was added, followed by stirring for 30minutes, whereupon pressure filtration was carried out under the sameconditions as above, to obtain a cake. The obtained cake was transferredto a flask, and a mixture comprising 54 g of EGMTBE, 54 g of TBA and 12g of water, was further added, followed by stirring for 30 minutes., toobtain a liquid (slurry) having the composite metal cyanide complexcatalyst (hereinafter referred to also as the DMC catalyst) dispersed inthe EGMTBE-TBA-water mixed solvent.

About 5 g of this slurry was put into a flask, roughly dried in anitrogen stream and then vacuum-dried at 80° C. for 4 hours. The solidwas weighed, whereby the concentration of the composite metal cyanidecomplex as the solid catalyst component, was 4.65 mass %. To the rest ofthe slurry, 120 g of polyol X was added and mixed, and then, thevolatile component was distilled off at 80° C. for 3 hours and furtherat 115° C. for 3 hours, to obtain a slurry-form catalyst (catalyst Y1).The concentration of the solid catalyst component in the slurry was 3.85mass %.

Reference Example 2

An aqueous solution comprising 10.2 g of zinc chloride and 10 g of waterwas put into a 500 mL flask. An aqueous solution comprising 4.2 g ofpotassium hexacyano cobaltate and 75 g of water was dropwise added tothe above aqueous zinc chloride solution in the flask over a period of30 minutes with stirring at a rate of 300 rpm (the number ofrotations/min). During this period, the mixed solution in the flask wasmaintained at 40° C. After completion of the dropwise addition of theaqueous potassium hexacyano cobaltate solution, the mixture in the flaskwas further stirred for 30 minutes, whereupon a mixture comprising 80 gof TBA, 80 g of water and 0.6 g of polyol X, was added, followed bystirring at 40° C. for 30 minutes and further at 60° C. for 60 minutes.The obtained mixture was subjected to filtration in the same manner asin Reference Example 1, to separate a solid (a cake) containing thecomposite metal cyanide complex.

Then, the obtained cake containing the composite metal cyanide complexwas transferred to a flask, and a mixture comprising 36 g of TBA and 84g of water was added, followed by stirring for 30 minutes, whereuponpressure filtration was carried out under the same conditions as above,to obtain a cake. The obtained cake was transferred to a flask, and amixture comprising 108 g of TBA and 12 g of water, was further added,followed by stirring for 30 minutes, to obtain a liquid (slurry) havingthe composite metal cyanide complex catalyst dispersed in the TBA-watermixed solvent.

About 5 g of this slurry was put into a flask, roughly dried in anitrogen stream and then vacuum-dried at 50° C. for 4 hours. The solidwas weighed, whereby the concentration of the composite metal cyanidecomplex as the solid catalyst component was 4.43 mass %. To the rest ofthe slurry, 120 g of polyol X was added and mixed, and then, thevolatile component was distilled off under reduced pressure at 50° C.for 2 hours and further at 60° C. for 5 hours, to obtain a slurry-formcatalyst (catalyst Y2). The concentration of the solid catalystcomponent in the slurry was 3.92 mass %.

Production of Polyol in 5 L Reactor

In Examples A1 to A11 (Examples A1 to A5 are working examples of theinvention, and Examples A6 to A11 are comparative examples), polyols Q1to Q11 were produced. As the reactor, a 5 L pressure resistant reactormade of stainless steel and equipped with a stirrer, was used.

The natures of the obtained polyols are shown in Table 1. Here, thehydroxyl value and the total unsaturated degree were measured by methodsin accordance with JIS K1557. Mw/Mn was measured by gel permeationchromatography (GPC) as calculated as polystyrene. The catalyst residuewas represented by the content of Zn and Co.

Example A1

Into the reactor, 587 g of polyol X as an initiator and 5.8 g ofcatalyst Y1 (containing 0.225 g of the solid catalyst component) wereput. The interior of the reactor was flushed with nitrogen, and then theinternal temperature was raised to 120° C., and 59 g of PO was added andreacted. After the pressure in the reactor once increased as PO wasadded, decreased, PO was supplied at a rate of 20 g/min in an amount of2,600 g, and thereafter, PO was supplied at a rate of 10 g/min in anamount of 1,300 g. During the supply of PO into the reactor, theinternal temperature of the reactor was maintained at about 120° C., andstirring was carried out at a rotational speed of 220 rpm to carry out apolymerization reaction. After completion of the reaction, heating andstirring were carried out at 120° C. for further 60 minutes to letunreacted PO react as far as possible. Then, deaeration under reducedpressure at 70° C. was carried out for 30 minutes, and then, nitrogengas was introduced to return the interior of the reactor to normalpressure.

To the obtained polyol, an aqueous solution containing 85% oforthophosphoric acid (H₃PO₄) was added, followed by vacuum-drying at120° C. to obtain polyol Q1 containing 3.0 ppm of orthophosphoric acid.

Example A2

Polyol Q2 was produced in the same manner as in Example A1 except thatthe content of orthophosphoric acid was changed to 5.5 ppm.

Example A3

Polyol Q3 was produced in the same manner as in Example A2 except thatas the catalyst, 5.7 g of catalyst Y2 (containing 0.225 g of the solidcatalyst component) was used, and instead of orthophosphoric acid, amixture (AP-8: 2-ethylhexyl acid phosphate, average molecular weight:266, manufactured by Daihachi Kagaku Kogyo KK) comprisingbis(2-ethylhexyl) phosphate [O═P(OH)(OC₈H₁₇)₂] and mono(2-ethylhexyl)phosphate [O═P(OC₈H₁₇) (OH)₂], was used and put in an amount such thatthe amount of phosphorus compound would be 15 ppm, based on the polyol.

Example A4

A polyol was produced in the same manner as in Example A1 except that asthe catalyst, 9.3 g of catalyst Y1 (containing 0.36 g of the solidcatalyst component) was used.

To the obtained polyol, an aqueous solution containing 85% oforthophosphoric acid was added, followed by vacuum drying at 120° C. toobtain polyol Q4 containing 8.5 ppm of orthophosphoric acid.

Example A5

A polyol was produced in the same manner as in Example A1 except that asthe catalyst, 2.32 g of catalyst Y1 (containing 0.090 g of the solidcatalyst component) was used.

To the obtained polyol, an aqueous solution containing 85% oforthophosphoric acid was added, followed by vacuum drying at 120° C. toobtain polyol Q5 containing 2.0 ppm of orthophosphoric acid.

Example A6

Polyol Q6 was produced in the same manner as in Example A1 except thatno orthophosphoric acid was added.

Example A7

Polyol Q7 was produced in the same manner as in Example A4 except thatno orthophosphoric acid was added.

Example A8

Polyol Q8 was produced in the same manner as in Example A5 except thatno orthophosphoric acid was added.

Example A9

Polyol Q9 was produced in the same manner as in Example A1 except thatinstead of orthophosphoric acid, phosphorus acid (H₃PO₃) was used.

Example A10

Polyol Q10 was produced in the same manner as in Example A3 except thatinstead of orthophosphoric acid, bis(2-ethylhexyl) phosphite[O═PH(OC₈H₁₇)₂] was used.

Example 11

Polyol Q11 was produced in the same manner as in Example A4 except thatinstead of orthophosphoric acid, tris(2-ethylhexyl) orthophosphate[O═P(OC₈H₁₇)₃] was used.

TABLE 1 Content of Kinetic phosphoric Hydroxyl viscosity UnsaturatedCatalyst acid value at 25° C. degree residue compound Ex. Polyol(mgKOH/g) Mw/Mn (mPa · s) (meq./g) (ppm) (ppm) A1 Q1 11.2 1.18 46500.0076 14.1 3.0 A2 Q2 11.4 1.20 4670 0.0075 13.7 5.5 A3 Q3 11.3 1.164570 0.0077 14.2 15 A4 Q4 11.4 1.14 4320 0.0071 22.1 8.5 A5 Q5 11.3 1.194980 0.0072 5.7 2.0 A6 Q6 11.5 1.18 4650 0.0076 14.5 0 A7 Q7 11.1 1.144320 0.0071 23.4 0 A8 Q8 11.7 1.19 4980 0.0072 5.2 0 A9 Q9 11.5 1.154450 0.0069 14.6 3.0 A10 Q10 11.4 1.18 4630 0.0070 14.8 15 A11 Q11 11.31.15 4330 0.0071 22.5 8.5Production of Isocyanate Group-Containing Urethane Prepolymer

Example B1

Into a 1 L reactor made of glass and equipped with a stirrer, 400 g ofpolyol Q1 was put. Deaeration under reduced pressure was carried out at120° C. for 2 hours, and flushing with nitrogen was further carried out.Then, the polyol in the reactor was cooled to 40° C. Into the reactor,tolylene diisocyanate (mixture of 2,4-isomer and 2,6-isomer, containing80 mass % of 2,4-isomer, trade name: TDI-80, manufactured by NipponPolyurethane Kogyo KK) was put in an amount such that the NCO indexbecame 200. While the content was stirred at a rotational speed of 100rpm, the reactor was heated to 90° C. over a period of 30 minutes andthen maintained at 90° C. for the reaction. For every predetermined timeduring the reaction, a part of the content was taken out, and thecontent z1 (mass %) of isocyanate groups was measured, whereupon theisocyanate reaction rate z (%) to the theoretical content z₀ (mass %) ofisocyanate groups, was obtained. Upon confirming that the content z₁(mass %) of isocyanate groups became at most the theoretical content z₀(0.84 mass %) of isocyanate group, the reaction was terminated to obtainan isocyanate group-containing urethane prepolymer.

The relation between the reaction time (hr) and the isocyanate reactionrate z (%) is shown in FIG. 1. Further, the viscosity at 25° C. of theobtained isocyanate group-containing urethane prepolymer, and theviscosity after maintaining it at 80° C. for 24 hours, are shown inTable 2.

Examples B2 to B11

An isocyanate group-containing urethane prepolymer was produced in thesame manner as in Example B1 except that the polyol as identified inTable 2 was used instead of polyol Q1. In the same manner as in ExampleB1, the relation between the reaction time (hr) and the isocyanatereaction rate z (%) is shown in FIG. 1. The viscosity at 25° C. of theobtained isocyanate group-containing urethane prepolymer and theviscosity after maintaining it at 80° C. for 24 hours, are shown inTable 2. Examples from B1 to B5 are working examples of the presentinvention, and Examples B6 to B11 are comparative examples.

TABLE 2 Viscosity after maintaining the Viscosity at prepolymer at 80°C. Ex. Polyol 25° C. (mPa · s) for 24 hours (mPa · s) B1 Q1 31000 31900B2 Q2 29700 30500 B3 Q3 29200 30400 B4 Q4 31200 32600 B5 Q5 30300 31900B6 Q6 38700 48000 B7 Q7 40200 54200 B8 Q8 36500 46200 B9 Q9 33400 38900B10 Q10 39800 54500 B11 Q11 41000 48600

As is evident from FIG. 1, with Q1 to Q5 being the polyether polyolcompositions of the present invention, the reaction with thepolyisocyanate proceeds at a moderate speed, whereby it is easy tocontrol the reaction. On the other hand, with Q6 to Q11, the reactionwith the isocyanate proceeds rapidly, whereby it is difficult to controlthe reaction. Further, as is evident from Table 2, isocyanategroup-terminated prepolymers prepared by using Q1 to Q5 being thepolyether polyol compositions of the present invention, are excellent instorage stability, while it is evident that the isocyanategroup-terminated prepolymers prepared by using Q6 to Q11, are poor inthe storage stability, as the viscosity after the storage tends toincrease.

The entire disclosure of Japanese Patent Application No. 2003-19062filed on Jan. 28, 2003 including specification, claims, drawings andsummary is incorporated herein by reference in its entirety.

What is claimed is:
 1. A method for producing a polyether polyolcomposition, which comprises: producing a polyether polyol byring-opening polymerization of an alkylene oxide in the presence of acomposite metal cyanide complex catalyst in such an amount that themetals derived from the composite metal cyanide complex catalyst wouldbe from 1 to 30 ppm based on the finally formed polyether polyol, andthen adding a phosphoric acid compound comprising a phosphoric acidselected from orthophosphoric acid, polyphosphoric acid andpolymetaphosphoric acid, and/or a partial ester of such a phosphoricacid, in an amount of from 0.5 to 100 ppm based on the polyether polyol,without removing the composite metal cyanide complex catalyst.
 2. Amethod for producing a polyether polyol composition which comprises:producing a polyether polyol containing 1-30 ppm of metals from acomposite metal cyanide complex by a ring-opening polymerization of analkylene oxide in the presence of a amount of a composite metal cyanidecomplex catalyst sufficient to provide 1-30 ppm of said metals in thepolyether polyol that is produced, and adding a phosphoric acid compoundcomprising a phosphoric acid selected from the group consisting of atleast one orthophosphoric acid, polyphosphoric acid andpolymetaphosphoric acid, and a partial ester thereof, in an amount offrom 0.5 to 100 ppm based on the polyether polyol; wherein saidpolyether polyol composition comprises: a polyether polyol, 0.5 to 100ppm based on the amount of polyether polyol of at least one phosphoricacid compound selected from the group consisting of at least oneorthophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, anda partial ester of orthophosphoric acid, polyphosphoric acid, orpolymetaphosphoric acid, and 1 to 30 ppm based on the amount ofpolyether polyol of at least one metal derived from a composite metalcyanide complex catalyst; and is produced by a ring-openingpolymerization of an alkylene oxide having at least three carbons in thepresence of a composite metal cyanide complex.
 3. A method for producingan isocyanate group-terminated prepolymer, comprising: performing aring-opening polymerization of an alkylene oxide in the presence of acomposite metal cyanide complex catalyst to form a polyether polyolcontaining from 1 to 30 ppm of metals derived from the composite metalcyanide complex based on the polyether polyol, adding to said polyetherpolyol a phosphoric acid compound selected from the group consisting ofat least one orthophosphoric acid, polyphosphoric acid,polymetaphosphoric acid, and a partial ester thereof, in an amount offrom 0.5 to 100 ppm based on the polyether polyol, and reacting thepolyether polyol composition with a polyisocyanate to form an isocyanategroup-terminated prepolymer; wherein said polyether polyol compositionis reacted with said polyisocyanate without first removing the compositemetal cyanide catalyst.
 4. A method for producing a polyurethane,comprising: performing a ring-opening polymerization of an alkyleneoxide in the presence of a composite metal cyanide complex catalyst toform a polyether polyol composition containing from 1 to 30 ppm ofmetals derived from said composite metal cyanide complex based on thepolyether polyol, adding to said polyether polyol a phosphoric acidcompound selected from the group consisting of at least oneorthophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, anda partial ester thereof, in an amount of from 0.5 to 100 ppm based onthe polyether polyol, and reacting the polyether polyol composition witha polyisocyanate to form a polyurethane; wherein said polyether polyolcomposition is reacted with said polyisocyanate without first removingthe composite metal cyanide catalyst.